CN114797510B - Preparation method and application of self-cleaning multi-dimensional material composite polymer self-supporting film - Google Patents
Preparation method and application of self-cleaning multi-dimensional material composite polymer self-supporting film Download PDFInfo
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
Abstract
The invention discloses a preparation method and application of a self-cleaning multidimensional material composite polymer self-supporting film, wherein the preparation method comprises the following steps: the PdNP-NH is prepared by adopting a sodium borohydride reduction method 2 -MILs-125 (Ti); bacterial cellulose is modified by dopamine hydrochloride to obtain PBC; ti is mixed with 3 C 2 T x Ultrasonic dispersing and then mixing with PdNP-NH 2 Mixing MIL-125 (Ti) and PBC, and vacuum filtering to obtain the self-supporting multi-dimensional material composite polymer membrane. The film has good stability, and one-dimensional linear PBC successfully uses three-dimensional granular PdNP-NH containing zero-dimensional palladium nano particles 2 MIL-125 (Ti) and two-dimensional Ti 3 C 2 T x The sheet layers are tightly connected, ti 3 C 2 T x Stable channels are formed between the sheet layers, high water flux is achieved, and high-efficiency removal of organic pollutants is realized, so that the method has great application in the field of water treatmentIs applied to the application value of (3).
Description
Technical Field
The invention relates to a preparation method and application of a polymer self-supporting film, in particular to a preparation method and application of a self-cleaning multi-dimensional material composite polymer self-supporting film.
Background
The membrane technology is an important high-new technology, and plays an important role in sustainable development strategy due to low cost, easy operation and relatively simple preparation process at present of shortage of energy supply, gradual shortage of resources and ecological deterioration. Therefore, in the treatment process of liquid pollutants, membrane separation technology is increasingly used, and the method has the advantages of high effluent quality, simplicity in operation and the like in the water treatment process due to the excellent performance of the membrane separation technology, so that the method is widely applied. At present, in the practical application process, the problems of easy pollution, poor reusability, low flux and the like of the membrane material are main factors for restricting the further development of the membrane material.
The separation membrane constructed by the one-dimensional material represented by the cellulose material, the separation membrane constructed by the two-dimensional material represented by the Mxene and the derivative thereof and the three-dimensional porous adsorption material Metal Organic Frameworks (MOFs) play different roles in the field of water treatment by the respective performance characteristics of the three materials.
The Metal Organic Frameworks (MOFs) are novel porous materials with ordered crystalline structures, and have the characteristics of high specific surface area, modifiable property and the like, and have potential application prospects in the field of adsorption water treatment. The titanium-based metal organic framework material is used as MOFs which take metal titanium ion clusters as connection nodes, has higher hydrothermal stability and excellent photocatalytic performance, and can be further applied to the catalytic degradation of organic pollutants. The mixed matrix membrane prepared by taking the titanium-based MOFs particles as the filler can effectively solve the problem of membrane defects caused by poor compatibility of the inorganic filler and the polymer substrate, thereby becoming a research hot spot in the field of membrane separation. The self-cleaning film has a certain self-cleaning effect by virtue of the excellent photocatalysis performance.
The bacterial cellulose is natural cellulose (BC) without any impurity, is very common in nature, is produced by fermenting sugar and plant polysaccharide by microorganisms, has the advantages of precise network structure, higher mechanical strength, higher water absorption and water retention performance and the like, is considered to be the cellulose with the best performance and highest use value, can be produced in large scale as a low-cost material, and becomes a hot spot for the research of the current membrane materials. However, in sewage treatment, bacterial cellulose membranes are susceptible to microbial corrosion, oxidation and contamination, resulting in degradation of membrane performance.
The two-dimensional material MXene is a graphene-like structure two-dimensional nano material, has large specific surface area and rich active sites, and has good dispersibility and reducibility, so that the material MXene has good potential in the fields of adsorption of organic pollutants in water and the like. Two-dimensional MXene phase Ti 3 C 2 T x The unique physicochemical properties of the material due to its unique lamellar structure have attracted a great deal of attention from many researchers, and two-dimensional MXene membranes for efficient solvent dehydration prepared therewith can have highly ordered 2D nanochannels, thus exhibiting excellent separation performance. However, the MXene material does not have photocatalytic performance, and the prepared film material is easy to pollute, so that the service life of the film material is reduced.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of a self-cleaning multi-dimensional material composite polymer self-supporting membrane for filtering organic pollutants; the invention also aims to provide the multi-dimensional material composite polymer self-supporting film with self-cleaning function and higher water flux, which is prepared by the method; the invention further aims to provide an application of the composite polymer self-supporting film in removing organic pollutants in sewage.
The technical scheme is as follows: the invention relates to a preparation method of a self-cleaning multi-dimensional material composite polymer self-supporting film, which comprises the following steps:
(1) NH of titanium-based metal organic framework material 2 Adding palladium nitrate (Pd (NO) 3 ) 2 ) Sodium borohydride (NaBH 4 ) Reducing palladium ions;
(2) Centrifuging, washing, and vacuum drying the sample to obtain three-dimensional granular palladium sodiumNanoparticle-supported metal organic framework material PdNP-NH 2 -MIL-125(Ti)；
(3) Dissolving Tris (hydroxymethyl) aminomethane (Tris) in pure water, mixing with a dilute hydrochloric acid solution, and preparing to obtain a Tris-HCl solution; adding Bacterial Cellulose (BC) to disperse in the Tris-HCl solution, adding dopamine hydrochloride, mixing and stirring.
(4) Centrifugally washing the mixed solution, and precipitating and diluting to obtain one-dimensional linear dopamine-coated bacterial cellulose (PBC);
(5) Mxene (Ti) 3 C 2 T x ) Ultrasonic treating in water, centrifuging, removing precipitate, and diluting to obtain two-dimensional lamellar Ti 3 C 2 T x ；
(6) The PdNP-NH 2 MIL-125 (Ti), PBC and two-dimensional lamellar Ti 3 C 2 T x Mixing, diluting with deionized water, performing ultrasonic stirring to obtain zero-dimensional, one-dimensional, two-dimensional and three-dimensional material composite dispersion liquid, and continuously stirring;
(7) And (3) laying a substrate at the bottom of a funnel of the vacuum suction filtration device in advance, then pouring the composite dispersion liquid, performing suction filtration to form a film, and airing the obtained sample to obtain the multi-dimensional material composite polymer self-supporting film with self-cleaning capability.
Further, the centrifugal rotating speed in the step (2) is 8000-8500r/min, and the centrifugal time is 5-10min; the washing process is to wash three times with N, N-dimethylformamide and acetone respectively, the vacuum drying temperature is 60-80 ℃, and the constant temperature time is 12-24 hours.
Further, in the step (3), the mass ratio of the tris (hydroxymethyl) aminomethane to the bacterial cellulose to the dopamine hydrochloride is 24-26:1:1-2, and the continuous stirring time is 8-12 hours.
Further, the centrifugal speed in the step (4) is 3000-3500r/min, the centrifugal time is 15-20min, and the precipitated PBC material is diluted to 2-6mg mL by pure water -1 。
Further, the ultrasonic time in the step (5) is 3-4 hours; the centrifugal rotating speed is 3000-3500r/min, the centrifugal time is 15-20min, the Ti is 3 C 2 T x Diluting the dispersion with pure water to 2-6mg mL -1 。
Further, the step (6) is to take PdNP-NH 2 Dispersing MIL-125 (Ti) powder in water solution by ultrasonic, adding magneton, stirring at 200-220r/min, then dripping PBC solution, stirring for 3-5min, and dripping Ti 3 C 2 T x Stirring the solution for 5-10min to obtain a multi-dimensional material composite dispersion; the PdNP-NH 2 MIL-125 (Ti), PBC and Ti 3 C 2 T x The mass ratio of the additive is 3-5:1:1.
the self-cleaning multi-dimensional material composite polymer self-supporting film prepared by the preparation method is a composite of zero-dimensional, one-dimensional, two-dimensional and three-dimensional materials.
The multi-dimensional material composite polymer self-supporting film can be applied to removing organic pollutants in sewage.
Design principle: three-dimensional MOF materials (e.g., NH 2 MIL-125 (Ti) and MOF-808) and two-dimensional nano-separation membranes (e.g., ti) 3 C 2 T x GO) is widely used due to its excellent catalytic properties (high specific surface area and photocatalytic properties) and mass transfer mechanisms (interlayer channels, nanopores and surface chemical modification). Due to bacterial cellulose and Ti 3 C 2 T x The band gap of the material is close to zero, the photocatalysis performance is almost negligible, the prepared film material has poor anti-pollution performance, serious film pollution phenomenon and short service life, the invention designs the film material for relieving the film pollution around the thought that the film can degrade the pollutant deposited on the surface, and introduces the photocatalyst NH 2 MIL-125 (Ti) and further improves the photocatalysis performance of the MIL-125 (Ti) by modification, so that the membrane material is endowed with excellent capability of degrading pollutants in visible light, namely, the photocatalysis performance of the composite membrane is endowed, and organic pollutants can be degraded, thereby improving the anti-pollution capability, slowing down the membrane pollution and realizing the self-cleaning performance.
In the multi-dimensional material composite polymer self-cleaning self-supporting film, dopamine modified bacterial cellulose and two-dimensional Ti 3 C 2 T x Material, pdNP-NH 2 MIL-125 (Ti) for extractingHigh material water flux, improved material circulation stability, and self-cleaning performance of membrane under visible light, palladium nanoparticles and NH 2 MIL-125 (Ti) constitutes a heterojunction, compared to pure NH 2 MIL-125 (Ti) with significantly improved photocatalytic performance. In addition, the invention leads the granular PdNP-NH to be prepared by ultrasonic and stirring 2 MIL-125 (Ti) can be uniformly wrapped with PBC and distributed in Ti 3 C 2 The Tx sheet layers can obtain continuous channels, reduce wrinkling, ensure more uniform distribution than other nano particles, and effectively solve the problem of pure granular PdNP-NH 2 MIL-125 (Ti) material is difficult to independently form a film, and meanwhile, the problem that the water flux is too small due to too tight stacking when a pure two-dimensional MXene material is formed into a film can be solved.
The composite polymer film of the invention is a two-dimensional layered PBC/Ti with special interlayer channels 3 C 2 T x /PdNP-NH 2 MIL-125 (Ti) composite film (two-dimensional layered material Ti 3 C 2 T x The interlayer channel of the self is added with a three-dimensional material PdNP-NH 2 MILs-125 (Ti) can enlarge the channel, increase the water flux, use one-dimensional material PBC can increase the stability of the membrane), water molecules can easily pass through, and most of the organic compounds are trapped on the membrane surface. After the deionized water is used for cleaning, the pollutant on the surface of the membrane still adheres to the surface of the membrane, but after the visible light irradiation is used for cleaning, pdNP-NH is used for cleaning 2 MILs-125 (Ti) is distributed on the surface of the membrane material with excellent photocatalytic capacity, and therefore, is able to remove most of the contaminants, exposing the membrane surface again.
The invention prepares a novel multidimensional self-cleaning composite polymer self-supporting film which combines PdNP-NH 2 Photocatalytic Properties of MIL-125 (Ti), ti 3 C 2 T x The advantages of the lamellar structure, the inclusion of PBC and the like, so that the membrane has lamellar structure, self-supporting property and self-cleaning property, and is higher than that of single one-dimensional material bacterial cellulose or single two-dimensional Ti 3 C 2 T x The feed flux of the formed membrane is obviously improved, and the pure three-dimensional particle material PdNP-NH 2 MIL-125 (Ti) is difficult to form into a film structure and is used inIn the filtering process, the three-dimensional granular materials are not strong in adhesion, the membrane is easy to loose and crack, and the filtering effect of the three-dimensional granular materials is equivalent to that of the acetate fiber base membrane.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) The multi-dimensional self-cleaning composite polymer self-supporting film prepared by the preparation method has good photocatalysis and self-supporting performance, high salt rejection rate and high water flux; the feeding flux can reach 482.4Lm -2 h -1 bar -1 Above, with two-dimensional Ti 3 C 2 T x The film is improved by about 12-15 times compared with the film, the pollution resistance is expected to be improved by about 1 time, and the service life is prolonged by 1 time; (2) The polymer self-supporting film also has good photocatalytic degradation performance, and the invention ensures that granular PdNP-NH is obtained by ultrasonic stirring 2 MIL-125 (Ti) can be uniformly wrapped with PBC and distributed in Ti 3 C 2 T x The continuous channel is obtained between the sheets, wrinkling is reduced, the prepared composite polymer membrane can improve water flux on one hand, and on the other hand, due to the introduction of the MOF-based photocatalyst, photocatalytic degradation performance of the membrane is provided, organic pollutants on the surface of the membrane can be effectively degraded under visible light, and the recycling of the composite membrane is achieved. Can be applied to industrial wastewater treatment, realizes high-efficiency filtration, can lighten the influence of surface pollutants on membrane performance in practical application, improves the membrane pollution problem, prolongs the service life of the membrane, reduces the cost, realizes the removal of small molecular organic pollutants, and is Ti 3 C 2 T x The application in the field of sewage treatment provides better prospect; (3) The preparation method is simple, the use is convenient, and the method can be applied to mass production.
Drawings
FIG. 1 shows a pure two-dimensional material Ti 3 C 2 T x A water contact angle test pattern of the film material;
FIG. 2 is a graph of water contact angle measurements of a one-dimensional material dopamine-modified bacterial cellulose membrane;
FIG. 3 is a PdNP-NH 2 -MILs-125 (Ti) transmission electron microscopy images;
FIG. 4 is a surface scanning electron microscope image of a PMM2 film;
FIG. 5 is a cross-sectional scanning electron microscope image of a PMM2 film;
FIG. 6 is a photograph of a PMM2 film after contamination;
FIG. 7 is a photograph of a PMM2 film after 2h illumination.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
A preparation method of a self-cleaning multi-dimensional material composite polymer self-supporting film comprises the following preparation steps:
1) 250mg of NH is taken 2 MIL-125 (Ti) was added at 20mL of 20mmol L -1 In palladium nitrate acetonitrile solution of (2), ultrasonic treatment for 10 minutes, stirring at room temperature for 16 hours, centrifuging at high speed, exchanging solvent with absolute ethyl alcohol again, repeatedly replacing for 5 times, transferring into a round bottom flask, adding 30mL of absolute ethyl alcohol, blowing for 10 minutes under argon atmosphere, and dropwise adding 50mL of 18mmol L -1 Reducing the sodium borohydride ethanol solution, and stirring for 10 minutes;
2) Centrifuging the sample obtained in the step 1) at a speed of 8500r/min for 5min, washing, vacuum drying, washing with N, N-dimethylformamide and acetone for three times respectively, and vacuum drying at 60deg.C for 24 hr to obtain three-dimensional granular material PdNP-NH 2 -MIL-125(Ti)；
3) Tris (2.423 g) was dissolved in 50mL of pure water, and reacted with 14mL of HCl (0.1 mol L) -1 ) The solutions were mixed and the volume was fixed at 100mL. Dispersing 0.1g of bacterial cellulose into the prepared Tris-HCl solution, and adding 0.1g of dopamine hydrochloride; putting a magneton into the mixed solution, and magnetically stirring for 10 hours;
4) Centrifuging the mixed solution obtained in the step 3) at 3300r/min for 18min, removing supernatant, and diluting the precipitated PBC material with pure water to 2mg ml -1 ；
5) Ti to be prepared 3 C 2 T x Adding the mixture into pure water, and performing ultrasonic treatment in a 350W ultrasonic instrument for 4 hours; then removing sediment and Ti according to the centrifugal speed of 3300r/min and the centrifugal time of 18min 3 C 2 T x The dispersion was diluted with pure water to 4mg mL -1 ；
6) Taking 16mg of PdNP-NH in step 2) 2 Ultrasonic dispersing MIL-125 powder in water solution, adding magneton 220r/min, stirring, dripping 2mL PBC solution in step 5), stirring for 3-5min, dripping 0.5mL Ti in step 5) 3 C 2 T x Stirring the solution for 10min to obtain a zero-dimensional, one-dimensional, two-dimensional and three-dimensional material composite dispersion liquid;
7) Pouring the multi-dimensional material composite dispersion liquid obtained in the step 6) into a filter bowl of a sand core filter device, wherein a cellulose acetate film (phi 47mm,0.22 mu m) is placed on a sand core filter head, and the mixture is subjected to suction filtration to form a film, and is dried for 20min at room temperature in a fume hood, and then the film is marked as PMM1.
The samples taken were analyzed and observed by a scanning electron microscope or the like, and the samples were used for studies on the separation performance and photocatalytic performance of the dye, and the results are shown in table 1.
According to Table 1, when the multi-dimensional material is used for simultaneous compounding, the two-dimensional material Ti 3 C 2 T x When the proportion of the dye to the three-dimensional material reaches 20 percent, the feeding flux in the RhB dye reaches 1055.1Lm -2 h -1 bar -1 The retention rate is 86 percent compared with pure two-dimensional Ti 3 C 2 T x Compared with the membrane, the three-dimensional material PdNP-NH is added 2 After MILs-125 (Ti) and one-dimensional material PBC, the rejection rate slightly decreased, although the membrane feed flux was significantly improved, with the membrane structure being incomplete as a whole.
Example 2
A preparation method of a self-cleaning multi-dimensional material composite polymer self-supporting film comprises the following preparation steps:
1) 250mg of NH is taken 2 MIL-125 (Ti) was added at 20mL of 20mmol L -1 Ultrasonic for 10min, stirring at room temperature for 16 hr, centrifuging at high speed, exchanging solvent with anhydrous ethanol again, repeatedly displacing for 5 times, transferring into round bottom flask, adding 30mL of anhydrous ethanol, blowing under argon atmosphere for 10min, and dropwise adding 50mL of 18mmol L -1 Reducing the sodium borohydride ethanol solution, and stirring for 10 minutes;
2) Will beCentrifuging the sample obtained in the step 1) at a speed of 8500r/min for 5min, washing, vacuum drying, washing with N, N-dimethylformamide and acetone for three times respectively, and vacuum drying at 60deg.C for 24 hr to obtain three-dimensional granular material PdNP-NH 2 -MIL-125(Ti)；
3) Tris (2.423 g) was dissolved in 48.21mL of purified water, and reacted with 14.7mL of HCl (0.1 mol L) -1 ) The solutions were mixed and the volume was fixed at 100mL. Dispersing 0.1g of bacterial cellulose into the prepared Tris-HCl solution, and adding 0.1g of dopamine hydrochloride; putting a magneton into the mixed solution, and magnetically stirring for 10 hours;
4) Centrifuging the mixed solution obtained in the step 3) at 3300r/min for 18min, removing supernatant, and diluting the precipitated PBC material with pure water to 2mg mL -1 ；
5) Ti to be prepared 3 C 2 T x Adding the mixture into pure water, and performing ultrasonic treatment in a 350W ultrasonic instrument for 4 hours; then removing sediment and Ti according to the centrifugal speed of 3300r/min and the centrifugal time of 18min 3 C 2 T x The dispersion was diluted with pure water to 4mg mL -1 ；
6) Taking 16mg of PdNP-NH in step 2) 2 Ultrasonic dispersing MIL-125 (Ti) powder in water solution, adding magneton 220r/min, stirring, dripping 2mL of PBC solution in step 5), stirring for 5min, dripping 1mL of Ti in step 5) 3 C 2 T x Stirring the solution for 10min to obtain a multi-dimensional material composite dispersion;
7) Pouring the multi-dimensional material composite dispersion liquid obtained in the step 6) into a filter cup of a sand core filter device with a sand core filter head and a cellulose acetate film (phi 47mm,0.22 mu m), filtering to form a film, and airing the film in a fume hood for 20min at room temperature, and marking the film as PMM2.
The samples taken were analyzed and observed by a scanning electron microscope or the like, and the samples were used for studies on the separation performance and photocatalytic performance of the dye, and the results are shown in table 1.
According to Table 1, when the multi-dimensional material is used for simultaneous compounding, the two-dimensional material Ti 3 C 2 T x When the ratio of the dye to the three-dimensional material reaches 40%, the feeding flux in the RhB dye reaches482.4Lm -2 h -1 bar -1 The retention rate of the membrane material is 100%, and compared with a single-dimensional material membrane, the membrane material has obviously improved feeding flux and retention rate after the multi-dimensional material is added.
Example 3
A preparation method of a self-cleaning multi-dimensional material composite polymer self-supporting film comprises the following preparation steps:
1) 250mg of NH is taken 2 MIL-125 (Ti) was added at 20mL of 20mmol L -1 Ultrasonic for 10min, stirring at room temperature for 16 hr, centrifuging at high speed, exchanging solvent with anhydrous ethanol again, repeatedly displacing for 5 times, transferring into round bottom flask, adding 30mL of anhydrous ethanol, blowing under argon atmosphere for 10min, and dropwise adding 50mL of 18mmol L -1 Reducing the sodium borohydride ethanol solution, and stirring for 10 minutes;
2) Centrifuging the sample obtained in the step 1) at a speed of 8500r/min for 5min, washing, vacuum drying, washing with N, N-dimethylformamide and acetone for three times respectively, and vacuum drying at 60deg.C for 24 hr to obtain three-dimensional material PdNP-NH 2 -MIL-125(Ti)；
3) Tris (2.423 g) was dissolved in 48.21mL of purified water, and reacted with 14.7mL of HCl (0.1 mol L) -1 ) The solutions were mixed and the volume was fixed at 100mL. Dispersing 0.1g of bacterial cellulose into the prepared Tris-HCl solution, and adding 0.1g of dopamine hydrochloride; putting a magneton into the mixed solution, and magnetically stirring for 10 hours;
4) Centrifuging the mixed solution obtained in the step 3) at 3300r/min for 18min, removing supernatant, and diluting the precipitated PBC material to 2mg mL -1 ；
5) Ti to be prepared 3 C 2 T x Adding the mixture into pure water, and performing ultrasonic treatment in a 350W ultrasonic instrument for 3-4 hours; then removing sediment and Ti according to the centrifugal speed of 3300r/min and the centrifugal time of 18min 3 C 2 T x The dispersion was diluted with pure water to 4mg mL -1 ；
6) Taking 16mg of PdNP-NH in step 2) 2 Ultrasonic dispersing MIL-125 (Ti) powder in water solution, adding magneton 220r/min stirring, dropwise adding 2mL of PBC solution in the step 5), stirring for 5min, and dropwise adding 1.5mL of Ti in the step 5) 3 C 2 T x Stirring the solution for 10min to obtain a multi-dimensional material composite dispersion;
7) Pouring the multi-dimensional material composite dispersion liquid obtained in the step 6) into a filter cup of a sand core filter device with a sand core filter head and a cellulose acetate film (phi 47mm,0.22 mu m), filtering to form a film, and airing the film in a fume hood for 20min at room temperature, and marking the film as PMM3.
The samples taken were analyzed and observed by a scanning electron microscope or the like, and the samples were used for studies on the separation performance and photocatalytic performance of the dye, and the results are shown in table 1.
According to Table 1, when the multi-dimensional material is used for simultaneous compounding, the two-dimensional material Ti 3 C 2 T x When the proportion of the dye to the three-dimensional material reaches 60 percent, the feeding flux in the RhB dye reaches 277.6Lm -2 h -1 bar -1 The rejection rate was 100%.
Example 4
A preparation method of a self-cleaning multi-dimensional material composite polymer self-supporting film comprises the following preparation steps:
1) 250mg of NH is taken 2 MIL-125 (Ti) was added at 20mL of 20mmol L -1 Ultrasonic for 10min, stirring at room temperature for 16 hr, centrifuging at high speed, exchanging solvent with anhydrous ethanol again, repeatedly displacing for 5 times, transferring into round bottom flask, adding 30mL of anhydrous ethanol, blowing under argon atmosphere for 10min, and dropwise adding 50mL of 18mmol L -1 Reducing the sodium borohydride ethanol solution, and stirring for 10 minutes;
2) Centrifuging the sample obtained in the step 1) at a speed of 8500r/min for 5min, washing, vacuum drying, washing with N, N-dimethylformamide and acetone for three times respectively, and vacuum drying at 60deg.C for 24 hr to obtain three-dimensional granular material PdNP-NH 2 -MIL-125(Ti)；
3) Tris (2.423 g) was dissolved in 48.21mL of purified water, mixed with 14.7mL of HCl (0.1M) solution, and the volume was fixed at 100mL. Dispersing 0.1g of bacterial cellulose into the prepared Tris-HCl solution, and adding 0.1g of dopamine hydrochloride; putting a magneton into the mixed solution, and magnetically stirring for 10 hours;
4) Centrifuging the mixed solution obtained in the step 3) at 3300r/min for 18min, removing supernatant, and diluting the precipitated PBC material with pure water to 2mg mL -1 ；
5) Ti to be prepared 3 C 2 T x Adding the mixture into pure water, and performing ultrasonic treatment in a 350W ultrasonic instrument for 4 hours; then removing sediment and Ti according to the centrifugal speed of 3300r/min and the centrifugal time of 18min 3 C 2 T x The dispersion was diluted with pure water to 4mg mL -1 ；
6) Taking 16mg of PdNP-NH in step 2) 2 Ultrasonic dispersing MIL-125 (Ti) powder in water solution, adding magneton 220r/min, stirring, dripping 2mL of PBC solution in step 5), stirring for 5min, dripping 2mL of Ti in step 5) 3 C 2 T x Stirring the solution for 10min to obtain a multi-dimensional material composite dispersion;
7) Pouring the multi-dimensional material composite dispersion liquid obtained in the step 6) into a filter cup of a sand core filter device with a sand core filter head and a cellulose acetate film (phi 47mm,0.22 mu m), filtering to form a film, and airing the film in a fume hood for 20min at room temperature, and marking as PMM4.
The samples taken were analyzed and observed by a scanning electron microscope or the like, and the samples were used for studies on the separation performance and photocatalytic performance of the dye, and the results are shown in table 1.
According to Table 1, when the multi-dimensional material is used for simultaneous compounding, the two-dimensional material Ti 3 C 2 T x When the ratio of the dye to the three-dimensional material reaches 80%, the feeding flux in the RhB dye reaches 175.8Lm -2 h -1 bar -1 The rejection rate was 100%.
Example 5
A preparation method of a self-cleaning multi-dimensional material composite polymer self-supporting film comprises the following preparation steps:
1) 250mg of NH is taken 2 MIL-125 (Ti) was injected at 20mL concentration of 20mmol L -1 Ultrasonic for 10min, stirring at room temperature for 16 hr, high-speed centrifuging, and againExchanging solvent with absolute ethanol, repeatedly displacing for 5 times, transferring into round bottom flask, adding 30mL of absolute ethanol, blowing under argon atmosphere for 10min, and dripping 50mL of 18mmol L -1 Reducing the sodium borohydride ethanol solution, and stirring for 10 minutes;
2) Centrifuging the sample obtained in the step 1) at a speed of 8500r/min for 5min, washing, vacuum drying, washing with N, N-dimethylformamide and acetone for three times respectively, and vacuum drying at 60deg.C for 24 hr to obtain three-dimensional granular material PdNP-NH 2 -MIL-125(Ti)；
3) Tris (2.423 g) was dissolved in 48.21mL of purified water, mixed with 14.7mL of HCl (0.1M) solution, and the volume was fixed at 100mL. Dispersing 0.1g of bacterial cellulose into the prepared Tris-HCl solution, and adding 0.1g of dopamine hydrochloride; putting a magneton into the mixed solution, and magnetically stirring for 10 hours;
4) Centrifuging the mixed solution obtained in the step 3) at 3300r/min for 18min, removing supernatant, and diluting the precipitated PBC material to 2mg mL -1 ；
5) Ti to be prepared 3 C 2 T x Adding the mixture into pure water, and performing ultrasonic treatment in a 300-400W ultrasonic instrument for 3-4 hours; then removing sediment and Ti according to the centrifugal speed of 3300r/min and the centrifugal time of 18min 3 C 2 T x The dispersion was diluted with pure water to 4mg mL -1 ；
6) Taking 16mg of PdNP-NH in step 2) 2 Ultrasonic dispersing MIL-125 (Ti) powder in water solution, adding magneton 220r/min, stirring, dripping 2mL of PBC solution in step 5), stirring for 3-5min, dripping 2.5mL of Ti in step 5) 3 C 2 T x Stirring the solution for 10min to obtain a multi-dimensional material composite dispersion;
7) Pouring the multi-dimensional material composite dispersion liquid obtained in the step 6) into a filter cup of a sand core filter device with a sand core filter head and a cellulose acetate film (phi 47mm,0.22 mu m), filtering to form a film, and airing the film in a fume hood for 20min at room temperature, and marking as PMM4.
The samples taken were analyzed and observed by a scanning electron microscope or the like, and the samples were used for studies on the separation performance and photocatalytic performance of the dye, and the results are shown in table 1.
According to Table 1, when the multi-dimensional material is used for simultaneous compounding, the two-dimensional material Ti 3 C 2 T x The proportion of the material to the three-dimensional material reaches 1:1, the feed flux in the RhB dye reaches 127.8Lm -2 h -1 bar -1 The rejection rate was 100%.
Comparative example 1
The preparation method of the multi-dimensional material composite polymer self-cleaning film comprises the following preparation steps:
1) 250mg of NH is taken 2 MIL-125 (Ti) was injected at 20mL concentration of 20mmol L -1 Ultrasonic for 10min, stirring at room temperature for 16 hr, centrifuging at high speed, exchanging solvent with anhydrous ethanol again, repeatedly displacing for 5 times, transferring into round bottom flask, adding 30mL of anhydrous ethanol, blowing under argon atmosphere for 10min, and dropwise adding 50mL of 18mmol L -1 Reducing the sodium borohydride solution, and stirring for 10 minutes;
2) Centrifuging the sample obtained in the step 1) at a speed of 8500r/min for 5min, washing, vacuum drying, washing with N, N-dimethylformamide and acetone for three times respectively, and vacuum drying at 60deg.C for 24 hr to obtain three-dimensional granular material PdNP-NH 2 -MIL-125(Ti)；
3) Taking 20mg of PdNP-NH in step 2) 2 Ultrasonic dispersing MIL-125 (Ti) powder in water solution, adding magneton 200-220r/min, stirring for 10min to obtain three-dimensional material dispersion;
4) Pouring the three-dimensional material dispersion liquid obtained in the step 3) into a filter bowl of a sand core filter device with a sand core filter head and a cellulose acetate film (phi 47mm,0.22 mu M), filtering to form a film, and airing the film in a fume hood at room temperature for 20min, and marking as M1.
The taken sample is analyzed and observed by a scanning electron microscope and the like, and the sample is used for researching the separation performance and the photocatalysis performance of the dye.
Comparative example 2
The preparation method of the one-dimensional material polymer film comprises the following steps:
1) Tris (2.423 g) was dissolved in 48.21mL of purified water, mixed with 14.7mL of HCl (0.1M) solution, and the volume was fixed at 100mL. Dispersing 0.1g of bacterial cellulose into the prepared Tris-HCl solution, and adding 0.1g of dopamine hydrochloride;
2) Taking the mixed solution obtained in the step 1), putting a magneton into the mixed solution, and magnetically stirring the mixed solution for 10 hours;
3) Centrifuging the mixed solution obtained in the step 2) at 3300r/min for 18min, removing supernatant, and diluting the precipitated PBC material with pure water to 2mg mL -1 ；
4) Dropwise adding 2ml of PBC solution in the step 3) into pure water, stirring for 5min, adding 220r/min of magneton, stirring for 10min, and obtaining a one-dimensional material dispersion;
5) Pouring the one-dimensional material dispersion liquid obtained in the step 4) into a filter bowl of a sand core filter device with a sand core filter head and a cellulose acetate film (phi 47mm,0.22 mu M), filtering to form a film, and airing the film in a fume hood at room temperature for 20min, and marking the film as M2.
The taken sample is analyzed and observed by a scanning electron microscope and the like, and the sample is used for researching the separation performance and the photocatalysis performance of the dye.
Comparative example 3
The preparation method of the two-dimensional material film comprises the following preparation steps:
1) The MXene (Ti 3 C 2 T x ) Ultrasonic treatment for 3-4 hr in 350W cell disruption instrument;
2) The material in the step 1) is centrifuged at 3300r/min for 18min, and the sediment and Ti are removed 3 C 2 T x The dispersion was diluted with pure water to 4mg mL -1 ；
3) Taking 2.5mL of Ti from step 2) 3 C 2 T x Dropping the solution into pure water, and stirring for 10min to obtain two-dimensional material dispersion;
4) Pouring the two-dimensional material dispersion liquid obtained in the step 3) into a filter bowl of a sand core filter device with a sand core filter head and a cellulose acetate film (phi 47mm,0.22 mu M), filtering to form a film, and airing the film in a fume hood at room temperature for 20min, and marking the film as M3.
Table 1 list and multidimensional material composite membrane Water flux and rejection Meter
Table 1 is a water flux and rejection table for the single-and multi-dimensional material composite membranes obtained under the experimental parameters. It can be seen that the pure two-dimensional Ti is ensured under the condition of complete interception 3 C 2 T x The feed flux of the membrane material to RhB is 35Lm -2 h -1 bar -1 In the following, the feed flux of the membrane material prepared from the multidimensional material to RhB is obviously improved, and the retention rate is also ensured.
The feeding flux of the composite polymer membrane material prepared by the invention can reach 482.4Lm -2 h -1 bar -1 The above (such as PMM 2), and two-dimensional Ti 3 C 2 T x The film has improved stain resistance by about 1 time and prolonged service life by about 1 time compared with the film which has been improved by about 12-15 times.
Application examples
Contact angle measurement: the prepared membranes (M2, M3) were placed on a horizontal stage of a tester, a drop of water was titrated onto the membranes perpendicular to the plane, images were collected with a computer, and data were obtained by processing on the computer.
Separation performance experiment:
the effective membrane area is 7.5cm -2 。
50mL of the contaminated solution (5 mg mL) -1 Rhodamine B) was poured into a filter bowl at the upper part of the prepared membrane, then vacuum pumped at a pressure of 1bar, the solution flowed through the membrane, and the filtrate was collected from the lower vessel. The filtrate volume and filtration time were recorded to calculate the permeability (Jp): j (J) w1 ＝V/AtP
Where A is the effective area of the membrane, V is the pure water volume, P is the pressure applied by the device, and t is the filtration time. The concentration of the components of the solution before and after separation was determined by means of an ultraviolet-visible spectrophotometer. The rejection rate is calculated by the following equation:
wherein C is filtrate The filtrate is the concentration of the filtrate, C feed Feed is the concentration of feed.
FIGS. 1 and 2 are respectively pure Ti obtained under the experimental parameters 3 C 2 T x The contact angles of the film and the pure bacterial fiber film are 66.5 degrees and 50.9 degrees, the contact angle is larger, and the hydrophilicity is required to be improved.
The contact angles of the PMM1, the PMM2 and the PMM3 prepared by the invention are about 20-40 degrees, and the hydrophilicity is obviously improved.
FIG. 3 is a PdNP-NH 2 MIL-125 (Ti) transmission electron microscope image, palladium nano particles are uniformly loaded on NH 2 -surface and interior of MILs-125 (Ti).
FIGS. 4 and 5 are scanning electron micrographs of the surface and cross section of a PMM2 membrane, respectively, showing that the surface can find channel-like void structures, the membrane surface is coated with dopamine-coated bacterial cellulose with a number of PdNP-NH 2 MILs-125 (Ti) materials, which are exposed to a large number of active sites, exhibit a distinct lamellar structure in cross section, and are more structurally stable.
Fig. 6 and 7 are photographs of the surface after surface contamination of the PMM2 film and after self-cleaning is completed, respectively.
Claims (7)
1. The preparation method of the self-cleaning multi-dimensional material composite polymer self-supporting film for removing organic pollutants in sewage is characterized by comprising the following steps of:
(1) NH of titanium-based metal organic framework material 2 -MILs-125 (Ti) is added to a palladium nitrate acetonitrile solution, and sodium borohydride is used to reduce palladium ions;
(2) Centrifuging, washing and vacuum drying the solution prepared in the step (1) to obtain a three-dimensional granular metal organic framework material PdNP-NH loaded by the zero-dimensional palladium nano particles 2 -MIL-125(Ti)；
(3) Dissolving Tris (hydroxymethyl) aminomethane in pure water, mixing with a dilute hydrochloric acid solution, and preparing to obtain a Tris-HCl solution; adding bacterial cellulose to disperse in the Tris-HCl solution, adding dopamine hydrochloride, mixing and stirring;
(4) Centrifugally washing the solution prepared in the step (3), and precipitating and diluting to obtain one-dimensional linear dopamine-coated bacterial cellulose PBC;
(5) Ti is mixed with 3 C 2 T x Ultrasonic treating in water, centrifuging, removing precipitate, and diluting to obtain two-dimensional lamellar Ti 3 C 2 T x ；
(6) Taking PdNP-NH 2 Dispersing MIL-125 (Ti) powder in water solution by ultrasonic, adding magneton, stirring at 200-220r/min, then dripping PBC solution, stirring for 3-5min, and dripping Ti 3 C 2 T x Stirring the solution for 5-10min to obtain a multi-dimensional material composite dispersion liquid, wherein the PdNP-NH is 2 MIL-125 (Ti), PBC and Ti 3 C 2 T x The mass ratio of the additive is 3-5:1:1, a step of;
(7) Laying a substrate in advance at the bottom of a funnel of a vacuum suction filtration device, then pouring the composite dispersion liquid, performing suction filtration to form a film, removing the substrate, and airing the obtained sample to obtain the multi-dimensional material composite polymer self-supporting film with self-cleaning capability;
the PdNP-NH 2 MIL-125 (Ti) is uniformly wrapped with PBC and distributed in Ti 3 C 2 T x And continuous channels are obtained between the sheet layers, so that wrinkling is reduced, and water flux is improved.
2. The method for preparing the self-cleaning multi-dimensional material composite polymer self-supporting film for removing organic pollutants from sewage according to claim 1, wherein the centrifugal speed in the step (2) is 8000-8500r/min, and the centrifugal time is 5-10 min.
3. The method for preparing a self-cleaning multi-dimensional material composite polymer self-supporting film for removing organic pollutants from sewage according to claim 1, wherein the washing process in the step (2) is three times of washing with N, N-dimethylformamide and acetone respectively, and the vacuum drying temperature is 60-80 ℃ and the constant temperature time is 12-24 hours.
4. The method for preparing the self-cleaning multi-dimensional material composite polymer self-supporting membrane for removing organic pollutants in sewage according to claim 1, wherein the mass ratio of the tris (hydroxymethyl) aminomethane to the bacterial cellulose to the dopamine hydrochloride in the step (3) is 24-26:1:1-2, and the continuous stirring time is 8-12 hours.
5. The method for preparing a self-cleaning multi-dimensional material composite polymer self-supporting membrane for removing organic pollutants from sewage according to claim 1, wherein the centrifugal speed in the step (4) is 3000-3500r/min, the centrifugal time is 15-20min, and the precipitated PBC material is diluted to 2-6mg mL with pure water -1 。
6. The method for preparing a self-cleaning multi-dimensional material composite polymer self-supporting film for removing organic pollutants in sewage according to claim 1, wherein the ultrasonic time in the step (5) is 3-4 hours; the centrifugal speed is 3000-3500r/min, the centrifugal time is 15-20min, the Ti is 3 C 2 T x Diluting the dispersion with pure water to 2-6mg mL -1 。
7. A self-cleaning multi-dimensional material composite polymer self-supporting film prepared by the preparation method of any one of claims 1-6, wherein the film is a composite of zero-dimensional, one-dimensional, two-dimensional and three-dimensional materials.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410223A (en) * | 2016-08-26 | 2017-02-15 | 南京理工大学 | Nitrogen doping carbonized bacterial cellulose/graphene/platinum composite nanomaterial and preparation method thereof |
| CN109632895A (en) * | 2019-01-18 | 2019-04-16 | 重庆大学 | Composite air-sensitive material and preparation method thereof and gas sensor and its application |
| JP2019118859A (en) * | 2017-12-28 | 2019-07-22 | 旭化成株式会社 | Noble gas separation membrane and method using the same for manufacturing noble gas with practically applicable purity |
| CN110270333A (en) * | 2019-05-28 | 2019-09-24 | 浙江工业大学 | A kind of bimetallic organic frame nano flower and its derivative and preparation method and application |
| CN111822028A (en) * | 2020-07-21 | 2020-10-27 | 西安工业大学 | Bismuth-based photocatalytic composite film based on MXene and preparation method thereof |
| CN111841655A (en) * | 2019-04-29 | 2020-10-30 | 南京理工大学 | Bacterial cellulose/polydopamine/titanium dioxide composite photocatalytic material and preparation method thereof |
| CN112516815A (en) * | 2020-11-10 | 2021-03-19 | 山东大学 | Flexible self-supporting MOF-GO membrane, preparation method thereof and application thereof in ion separation and dye removal |
| CN113058436A (en) * | 2021-03-15 | 2021-07-02 | 上海应用技术大学 | Graphene-based Ag @ ZIF-67 composite material film and preparation method and application thereof |
-
2022
- 2022-04-14 CN CN202210388700.7A patent/CN114797510B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410223A (en) * | 2016-08-26 | 2017-02-15 | 南京理工大学 | Nitrogen doping carbonized bacterial cellulose/graphene/platinum composite nanomaterial and preparation method thereof |
| JP2019118859A (en) * | 2017-12-28 | 2019-07-22 | 旭化成株式会社 | Noble gas separation membrane and method using the same for manufacturing noble gas with practically applicable purity |
| CN109632895A (en) * | 2019-01-18 | 2019-04-16 | 重庆大学 | Composite air-sensitive material and preparation method thereof and gas sensor and its application |
| CN111841655A (en) * | 2019-04-29 | 2020-10-30 | 南京理工大学 | Bacterial cellulose/polydopamine/titanium dioxide composite photocatalytic material and preparation method thereof |
| CN110270333A (en) * | 2019-05-28 | 2019-09-24 | 浙江工业大学 | A kind of bimetallic organic frame nano flower and its derivative and preparation method and application |
| CN111822028A (en) * | 2020-07-21 | 2020-10-27 | 西安工业大学 | Bismuth-based photocatalytic composite film based on MXene and preparation method thereof |
| CN112516815A (en) * | 2020-11-10 | 2021-03-19 | 山东大学 | Flexible self-supporting MOF-GO membrane, preparation method thereof and application thereof in ion separation and dye removal |
| CN113058436A (en) * | 2021-03-15 | 2021-07-02 | 上海应用技术大学 | Graphene-based Ag @ ZIF-67 composite material film and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 含Zr、Ti等具有光催化活性的金属有机骨架材料（MOFs）的合成、改性及调变;沈丽娟;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20180515;正文第77页 * |
| 葛金龙等.《金属有机骨架材料制备及其应用》.中国科学技术大学出版社,2019,第210页. * |
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